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Electrochemical oxidative aminocarbonylation of terminal alkynes


Palladium-catalysed oxidative carbonylation using oxygen as the oxidant is an economical approach; however, the gas mixture of CO and air has an explosive limit of 12.5–74.0% that could hamper extensive application of this process. Herein we report an electrochemical aminocarbonylation of alkynes under atmospheric pressure in an undivided cell without an external oxidant. The transformation has a broad substrate scope (83 examples) that involves primary amines and ammonium salts. Furthermore, mechanistic studies through cyclic voltammetry, in situ infrared and quick-scanning X-ray absorption fine structure spectroscopy reveal the reasons for this protocol proceeding smoothly under electrochemical conditions.

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Fig. 1: Electrochemical oxidative aminocarbonylation of terminal alkynes.
Fig. 2: Cyclic voltammetry studies.
Fig. 3: In situ infrared studies.
Fig. 4: XAFS studies.
Fig. 5: Mechanistic investigation.
Fig. 6: The substrate scope for the aminocarbonylation of primary and secondary amines.
Fig. 7: The substrate scope for the aminocarbonylation of ammonium salts.

Data availability

All data including experimental procedures and compound characterization are available within the paper and its Supplementary Information. All other data are available from the authors on reasonable request.


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This work was supported by the National Natural Science Foundation of China (grant nos. 21520102003, 21702152), the 973 Program (grant no. 2012CB725302), the CAS Interdisciplinary Innovation Team and the Hubei Province Natural Science Foundation of China (grant no. 2017CFA010). The Program of Introducing Talents of Discipline to Universities of China (111 Program) is also appreciated. X-ray absorption spectroscopy analysis was performed at the National Synchrotron Radiation Research Center (44A in Taiwan Photon Source). We would like to thank O. Muller from Bergische University Wuppertal for providing JAQ Analyzes QEXAFS software for analysing Quick-XAFS data. We would like to thank G. Li from State Utah University and S. Tang from the Weizmann Institute of Science for advising on the manuscript.

Author information




A.L., Y.-H.C. and L.Z. contributed to the conception and design of the experiments. H.L., Jingcheng H., D.Z., Jiayu H., P.P., S.W., R.S., J.P., C.-W.P., J.-L.C., J.-F.L. and H.Z. performed the experiments. L.Z., Y.-H.C. and A.L. co-wrote the manuscript and all authors contributed to data analysis and scientific discussion.

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Correspondence to Yi-Hung Chen or Aiwen Lei.

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Supplementary Information

Supplementary Methods, Tables 1–6, Figs. 1–36 and references.

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Zeng, L., Li, H., Hu, J. et al. Electrochemical oxidative aminocarbonylation of terminal alkynes. Nat Catal 3, 438–445 (2020).

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